Lithium Hydroxide → HCID 86663673, compound

HRID 1193240Notes

Reaction equation

HRID 1193240 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[CH:14]=[CH:13][C:12]([CH:15]2[CH2:17][CH2:16]2)=[C:11]([CH:18]=[C:19]2[C:23]([CH3:25])([CH3:24])[O:22][C:21]([CH3:27])([CH3:26])[C:20]2=[O:28])[CH:10]=1.[OH-:29].[Li+]>CO.OO>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[CH:14]=[CH:13][C:12]([CH:15]2[CH2:17][CH2:16]2)=[C:11]([CH:18]2[C:19]3([C:20](=[O:28])[C:21]([CH3:27])([CH3:26])[O:22][C:23]3([CH3:24])[CH3:25])[O:29]2)[CH:10]=1

Participants

5

Reactant 2

HCID 3939Lithium HydroxideHCID 66823579HCID 66823579, compound

Product 1

HCID 86663673HCID 86663673, compoundYield 429.9%

Reagents, catalysts & solvents 2

HCID 784Hydrogen PeroxideCatalystHCID 887MethanolSolvent

Procedure

To a solution of 4-[1-(2′,4′-dichloro-4-cyclopropylbiphenyl-3-yl)-methylidene]-2,2,5,5-tetramethyldihydrofuran-3-one (20.0 g, 0.048 mol) in methanol (800 ml) at 35° C. is added 50% aqueous hydrogen peroxide (4.80 ml, 0.072 mmol), followed immediately by 2M lithium hydroxide (4.80 ml, 9.60 mmol) solution. The mixture is stirred at this temperature for a further 2 hours, then allowed to cool to room temperature. Then reaction mixture is quenched with 10% sodium metabisulfite (negative KI-starch indicator test) then diluted with diethyl ether. Most of the methanol is removed under vacuum, and the crude mixture is partitioned between distilled water and diethyl ether. The aqueous phase is further extracted with diethyl ether (×2), then all organics are combined and washed with saturated sodium bicarbonate (×2) then brine. After drying over magnesium sulfate the suspension is filtered and the filtrate concentrated in vacuo to afford 2-(2′,4′-dichloro-4-cyclopropylbiphenyl-3-yl)-4,4,6,6-tetramethyl-1,5-dioxa-spiro[2.4]heptan-7-one (17.80 g) as an orange foam. This material is of sufficient purity to use directly in the next step without further purification.

Workup

  1. customThen reaction mixture
  2. customis quenched with 10% sodium metabisulfite (negative KI-starch indicator test)
  3. additionthen diluted with diethyl ether
  4. customMost of the methanol is removed under vacuum
  5. customthe crude mixture is partitioned
  6. distillationbetween distilled water and diethyl ether
  7. extractionThe aqueous phase is further extracted with diethyl ether (×2)
  8. washwashed with saturated sodium bicarbonate (×2)
  9. dry with materialAfter drying over magnesium sulfate the suspension
  10. filtrationis filtered
  11. concentrationthe filtrate concentrated in vacuo

Sources & evidence

ORD record
ord-c36a2475df6d468481c023739d073d95
Source dataset
uspto-grants-2014_03
Patent number
US08680299B2

Reaction notes

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